Diester of thiodipropionic acid



United States Patent 0 ice 1 Claim. (Cl. 260481) ABSTRACT OF THE DISCLOSURE The diester of thiodipropio-nic acid and 3-hydroxy-2,2,4- trimethylpentyl isobutyrate useful as a stabilizer for plastic materials subject to oxidative degradation.

This application is a division of Serial No. 212,485, filed July 25, 1962, now U.S. Patent No. 3,282,890, issued November 1, 1966.

This invention relates to normally solid poly-a-olefins and to the problem of protecting them against oxidative degradation, particularly under elevated temperature conditions.

Normally solid polymers of a-olefins, generally referred to herein as POlY-CL-Olfifil'lS, such as, for example, normally solid polyethylene, normally solid polypropylene and the like, are prone to oxidative degradation. This is particularly true at elevated temperatures, that is, temperatures above 20 C. This degradation involves rupture of the polymer chains and formation of carbonyl (:C=O) groups. Evidence of such degradation in its early stage is the presence of peroxides. As this degradation progresses, articles and coatings containing these polymers at large concentrations tend to crack, become brittle and lose tensile strength to the extent of mechanical failure.

Normally solid poly-u-olefins are commonly exposed to elevated temperatures in making useful compositions and articles out of resins containing them, and also in normal uses of some of these compositions and articles. Thus, such customary processing procedures as roll compounding, injection molding, extrusion and the like involve elevated temperatures. In such end uses as electrical insulation, protective coatings for electrical wire, plastic pipes for hot water and steam, and the like, elevated temperatures are frequently normally encountered. Hence, when normally solid poly-ot-olefins, particularly isotactic or crystalline polymers such as isotactic or crystalline polypropylene and the like, and compositions containing them are subjected to these procedures and employed in such end uses, oxidative degradation of the poly-a-olefins takes place.

This invention is based upon the discovery of the 3-hydroxy-Z,2,4-trimethylpentyl isobutyrate diester of 3,3- thiodipropionic acid and its utility as a poly-a-olefin stabilizer, as a synergist for other poly-a-olefin stabilizers and as a plasticizer for resins such as poly-ot-olefins generally and particularly for crystalline polymers such as isotactic polypropylene.

This invention, in summary, comprises as a new composition of matter the diester of 3,3-thiodipropionic acid and 3-hydroxy-2,2,4-trimethylpentyl isobutyrate. In addition, this invention comprises a normally solid, poly-otolefin composition containing the diester of 3,3-thiodipropionic acid and 3-hydroxy-2,2,4-trimethylpentyl isobutyrate at a protective concentration.

The diester of 3,3-thiodipropionic acid and 3-hydroxy- 2,2,4-trimethylpentyl isobutyrate is a pale yellow liquid at 20 C. with an APHA color of 175. It has a boiling point range of 140165 C. at a pressure of 9 microns of mer- Patented Oct. 29, 1968 cury. The theoretical molecular Weight of the diester is about 574. It has a sulfur content of 5.6% by weight and a saponification equivalent of 143.2.

The diester of 3,3-thiodipropionic acid and 3-hydroxy- 2,2,4-trimethylpentyl isobutyrate is readily made by refiuxing together a suitable esterification catalyst, 3,3- thiodipropionic acid and 3-hydroxy-2,2,4-trimethylpentyl isobutyrate (also referred to as 2,2,4-trimethyl-1,3-pen tanediol monoisobutyrate or as T MPD-MI) at a mole ratio of said monoisobutyrate to the thiodipropionic acid of at least about 2:1. The 3-hydroxy-2,2,4-trimethylpentyl isobutyrate is readily prepared by refluxing together a suitable esterification catalyst, isobutyric acid and 2,2,4- trimethyl-1,3-pentanediol at a mole ratio of the diol to the acid of about 1: 1. Preferably, in both esterification procedures, the desired ester in each case is removed by conventional ways and means from the esterification reaction mixture.

The normally solid, poly-ot-olefin composition of this invention comprises a normally solid resin portion and dispersed therein the diester of '3,3'-thiodipropionic acid and 3-hydroxy-2,2,4-trimethylpentyl monoisobutyrate. The resin portion consists essentially of at least one normally solid, poly-u-olefin polymer.

A normally solid, poly-a-olefin polymer is a polymer derived from an a-monoolefinic hydrocarbon having 2-10 carbon atoms. Such a polymer is provided by the normally solid homopolymers of a-monoolefinic hydrocarbons having generally 2-10 carbon atoms, preferably 26 carbon atoms and usually 2-4 carbon atoms. It is also provided by the normally solid copolymers (which include graft polymers, addition polymers, block and the like) of m-monoolefinic hydrocarbons having generally 210 carbon atoms, preferably 26 carbon atoms and usually 2-4 carbon atoms, as Well as of these monoolefinic hydrocarbons and other compounds.

Examples of a normally solid polymer derived from an u-rnonoolefinic hydrocarbon having 2-10 carbon atoms are the linear and branched, low density and high density, crystalline and amorphous, normally solid, homopolymers and copolymers of ethylene, propylene, butene-l, isobutylene, pentene-l, 2-methylbutene-1, 3-methylbutene-1, hexene-l, heptene-l, octene-l, nonene-l, decene-l, 4- methylpentene-l, 4-methylhexene-1, S-ethylhexene-l, 6- methylheptene-l, 6-ethylheptene-1, styrene, allyl benzene and the like. Processes for preparing normally solid polya-olefin polymers are well-known and described in detail in the prior art. See, for example, the U.S. Patent, No. 2,153,553, to Fawcett et al., the U.S. Patent, No. 2,912,- 429, to Cash, and the U.S. Patent, No. 2,917,500, to Hagerneyer et al. In general, a normally solid, poly-a-olefin polymer is a thermoplastic material which at 20 C. is solid. It includes the so-called poly-a-olefin waxes which usually have average molecular Weights in a range from about three thousand to about twelve thousand.

The normally solid resin portion, in addition to at least one normally solid, poly-a-olefin polymer, can also comprise other polymeric or resinous components. Thus, it can comprise a normally solid polymer derived from another a-monoolefinic hydrocarbon having generally 210 carbon atoms. It can comprise a different kind of polymer, which may be desired as a physical property improver.

The normally solid, poly-a-olefin composition can also comprise one or more other antioxidants, ultraviolet light inhibitors, anticorrosion additives, antistatic agents, foaming agents, additional plasticizers, pigments, mold release agents, slip agents, fillers, extenders and the like including physical property improvers other than polymeric compounds. As a matter of fact, preferred embodiments of the poly-et-olefin composition of this invention comprise not only a poly-a-olefin resin portion and the diester of 3,3-thiodipropionic acid and 3-hydroxy-2,2,4- trimethylpentyl isobutyrate, but also a sterically hindered phenol type antioxidant which forms with the diester a synergistic, poly-a-olefin stabilizing mixture. Typical hindered phenol type antioxidants include bisphenols such as an alkylidenebis(alkylphenol), a thiobisphenol and the like, and an alkyl phenol such as a 2,6-dialkyl-p-cresol and the like. Examples of a hindered phenol type antioxidant include:

2,6-di-tert. butyl-p-cresol 2,2'-methylenebis[6(1-methylcyclohexyD-p-cresol] 4,4'-butylidenebis(6-tert. butyl-m-cresol) 4,4-thiobis(6-tert. butyl-m-cresol) The weight ratio of the diester to the hindered phenolic antioxidant generally is in a range from about 1:20 to about 20:1 with the preferred range being from about 1:10 to about 10:1.

Concentration of the diester of 3,3-thiodipropionic acid and 3-hydroxy-2,2,4-trimethylpentyl isobutyrate in the poly-a-olefin composition of this invention in general depends upon the degree of stabilization desired and the degree of plasticization desired. The degree of stabilization depends upon processing conditions and subsequent environmental conditions to which the poly-a-olefin composition is to be exposed. In general, however, a concentration of the diester generally in a range from about 0.01 to about 10% by weight of the total poly-m-olefin polymeric content of the composition and preferably in a range from about 0.05 to about 5% by weight of the total poly-a-olefin polymeric content is an effective concentration for most end uses of the composition. In general, Within these ranges, the higher the concentration of the diester, the more plasticized is the resin portion of the composition.

The normally solid, poly-a-olefin composition of this invention is prepared by incorporating the diester of 3,3'-thiodipropionic acid and 2,2,4-trimethylpentyl isobutyrate into the normally solid resin portion of the composition. Generally, such incorporation is performed by any one of a number of known methods such as roll compounding, extrusion, solvent mixing and the like. For example, such incorporation can be performed by heating or otherwise softening the normally solid resin portion to a workable consistency and then Working in, as by roll compounding, the diester until a substantially uniform mixture or dispersion is obtained. Another typical procedure is to dissolve the additives in a low boiling solvent such as, for example, acetone, and, after thoroughly mixing the resulting solution with the resin portion of the composition, which may be in fiake or other such form, evaporating the solvent. While the components of the synergistic mixture of this invention are preferably incorporated together into the resin portion of the composition, it is within the scope of this invention to incorporate them separately into the resin portion. In addition, while it is preferred that the stabilizer of this invention be incorporated into the resin portion at the same time as other additives are normally incorporated into said portion, it is within the scope of this invention to undertake such incorporation at any time.

The poly-a-olefin composition of this invention is useful in coatings and as materials of construction for shaped articles. Thus, it can be made into various shaped articles, such as, for example, pellets, sheeting, films, bars, tubes, pipes, filaments, fibers, specially shaped structural elements and the like as by conventional casting and molding techniques which include extrusion, blow molding and the like.

The diester of 3,3'-thiodipropionate and 2,2,4-dimethyl- 1,3-pentanediol monoisobutyrate alone and in combination with other poly-a-olefin stabilizers, upon incorporation into polya-olefins, results in compositions of outstanding stability and, particularly in the case of crystalline polypropylene, improved low temperature properties. In this regard, crystalline polypropylene is not suitable for use in many applications because of its high brittle point. Brittle point is the temperature at which the polymer exhibits brittle failure under specific impact conditions as measured by the ASTM Test D746SST. Because of polypropylenes relatively poor performance at low temperatures, its utility as a packaging material for frozen foods, wire and cable, plastic pipe, etc., has been limited. Addition of the diester of this invention to crystalline polypropylene substantially reduces its brittle point to practical levels. Hence, poly-a-olefins and particularly crystalline polypropylene stabilized in accordance with this invention have extended life expectancy and can be used more effectively and broadly than unstabilized poly-a-olefins and particularly crystalline polypropylene.

This invention is further illustrated by thefollowing examples of various aspects thereof, including specific embodiments. This invention is not limited to these specific embodiments unless otherwise indicated.

Example 1 This example illustrates the preparation of the diester of 3,3-thiodipropionic acid and 2,2,4-trimethylpentyl iosbutyrate.

A mixture consisting essentially of 534 grams (3 moles) of 3,3'-thiodipropionic acid, 1620 grams (7.5 moles) of 2,2,4 trimethyl 1,3 pentanediol monoisobutyrate, 200 grams of xylene and 1.0 gram (0.004 mole) of dibutyl tin oxide is prepared and heated to refiux in a suitable esterification reactor having a water separator. After 20 hours of refluxing, typically about 108 grams (6.0 moles) of Water is obtained. The reaction mixture in the reactor is then treated with steam at C. to remove therefrom low boiling material and thereafter admixed with a 5% by weight, aqueous, caustic solution. The organic layer that forms is removed, dried and filtered, giving 1600 grams (2.8 mole) of the diester of 3,3'-thiodipropionic acid and 3-hydroxy-2,2,4-trirnethylpentyl isobutyrate. This represents a 92% yield based on the 3,3'-thiodiprop-ionic acid.

Specific embodiments of the poly-u-olefin composition of this invention are formulated as follows.

Example 2.Polypropylene composition Components: Parts by wt.

Resin portion Normally solid crystalline polypropylene 1000 Additives portion Diester of 3,3'-thiodipropionic acid and 3-hy- Additives portion Diester of 3,3'-thiodipropionic acid and 3-hydroxy-2,2,4-trimethylpentyl isobutyrate 5 4,4-butylidenebis(6-tert. butyl-m-cresol) 1 Example 4.-Polypropylene composition Components: Parts by Wt.

Resin portion Normally solid polypropylene 1000 Additives portion Diester of 3,3-thiodipropionic acid and 3-hydroxy-2,2,4-trimethylpentyl isobutyrate 5 4,4-butylidenebis(6-tert. butyl-m-cresol) 3 Example 5.Polypropylene composition Components: Parts by Wt.

Resin portion Normally solid polypropylene 1000 Additives portion Diester of 3,3-thiodipropionic acid and 3-hydroxy-2,2,4-trimethylpentyl isobutyrate 5 4,4-thiobis(6-tert. butyl-m-cresol) Example 6.Polypropylene composition Components: Parts by wt.

Resin portion Normally solid polypropylene 1000 Additives portion Diester of 3,3'-thiodipropionic acid and 3-hy- 6 Example 11.Low brittle point, crystalline polypropylene composition Components: Parts by wt.

Resin portion Crystalline polypropylene 95 Additives portion 4 ggigfiigig? gz g if gfgzgB Diester of 3,3-thiodipropionic acid and 3-hyhydroxy-Z,2,4-trimethylpentyl isobutyrate 5 Example 7.Polypropylene composition 2: fi i g g Pans by Example 12.Low brittle point, crystalline polypropylene com sitio Normally solid polypropylene 1000 p0 n Add tives portion u Components: Parts y Diester of 3,3 -th1od1prop1on1c acid and 3-hy- 1o Resin portion Q Y'? y P Y lsobutyrate 5 Crystalline polypropylene 90 2,6-d1tert1ary butyl-p-cresol 1 Additives portion Example 8 -P01ypropy1ene composition Diester of 3,3-thiodipropionic acid and 3-hydrox -224-trim h l t Components: Parts by wt. Y (it y pen yl isobutyrate 10 Resin portion PF Y scfhd P YP PY 1000 Compositions of Examples 2-10 ar prepared, for ex- Addttlves P IH H ample, by mixing the normally solid polypropylene with Dlestel' 0f P P E acld and 3" an acetone solution of the additives portion and thereafter Q Y-?, ll P Y lsobutyfatfi 5 evaporating the acetone by placing the mixture in a vac- 2,6'd1teTt1a1'Y y 'P' e501 3 uum oven at 70 C, for one hour,

Example 9.Polypropylene composition Compositions of the Examples 11 and 12 are prepared in each case by milling the crystalline polypropylene with f Parts by the diester at 190 C. for 10 minutes.

porltllon lid 1 The stabilities of the Examples 2-10 embodiments of A 9? y 9 Po ypropylene 1000 the poly-a-olefin composition of this invention are demorr d lnves z strated by the following data obtained in the stability Dlgster a 2 10 fi f i and testing of samples of these compositions and samples of Y' i1 g g pentylhlso utyrate 5 similar polypropylene compositions. In these tests, samfillet ylene (1 ylcyclohexyn'p ples of the compositions were placed in aluminum dishes Creso 1 1 and subjected to heat at 185 C. in a forced draft oven. Example 10.-Polypropylene composition Samples were removed at intervals of time indicated in Components: Parts by Wt the following Table I and a comparlson of their colors Resin Portion made with a sheet of 8 standard colors ranging from white, Normally Solid Polypropylene 1000 which was rated as 1, to dark brown WhlCh was rated as 8. Additives Portion The polypropylene employed in these tests in each case Diester f 33'4hiodiProPionic acid and was a crystalline polypropylene having an lnherent viscosdroxy-2,2,4-trimethylpentyl isobutyrate 5 y of and Ineltlng P 0f 2,2 methylenebis[6(1- methylcyclohexy1)-p- The test results and other test conditions in this series cresol] 3 of tests are tabulated in the following Table I.

TABLE I Concentration Color of Sample After Sample Additive(s) (Percent by No. weight of 8 hours 16 hours 24 hours poly-a-olefin) 1 Diestcr of 3,3-thiodipropionic acid and 3-hy- 0.5 2 4 5 droxy-2,2,4-tri-methylpenty1 isobutyrate. 2..- Dilauryl 3,3'-thiodipropionate 0. 5 4 5 8 4,4-butylidenebis(6-tert. butyl-m-cres0l). 0. 5 4 5 6 Dilauryl3,3-thiodipropionate 4-4butylidenebis 0.5 2 3 6 (ti-tart. butyl-m-cresol) 0. 1 5 .o Diester of 3,3-thiodipropionic acid and 3-hy- 0 5 d1'oxy-2,2,-trirnethylpentyl isobutyrate. 1 2 3 4 4,4-butylidenebis(fi-tert. butyl-rn-cresol) Diester of 3,3-thiodipropionic acid and 3-hy- 1 0 5 droxy-2,2,4-trimethylpentyl isobutyrate. 3 2 2 3 4,4-butylidenebis(fi-tert. butyl-m'cresol) .ll 4,4'-thiobis(6-tert. butyl-m-eresol) 0. 5 4 5 7 Diester of 3,3-thiodipropionic acid and 3-hy- 0 5 draw-2,2,4-trimethylpentyl isobutyrate. 1 2 3 4 4,4'-thiobis(6-tert. butyl-m-cresol) 9 Diester oi 3,3-thiodipropionio acid and 3-hy- 0 5 droxy-2,2,4-trimethylpentyl isobutyrate. 3 2 2 4 4,4-thiobis(6-tert. butyl-m-cresol) 10 2,6-ditertiary butyl-p-cresol 0.5 5 6 8 11 Diester of 3,3-thiodipropionic acid and 3-hy- 0 5 droxy-2,2,4-trimethylpentyl isobutyrate. 1 2 3 4 2,6-ditertiary butyl-p-cresol s 12 Diester of 3,3-thiodipropionic acid and 3-hy- 0 5 droxy-Z,2,4-trimethylpentyl isobutyrate. 3 2 3 3 2,6ditertiary butylp-cresol s 13 2,2-methylenebis[6(l-methylcyclohexyl)-p- 5 5 6 cresol]. 0.5 14 Diester of 3,3-thiodipropionic acid and 3-hydroxy-2,2,4-trimethy1pentyl isobutyratet 0. 5 2 4 4 2,2-me1t]hylenebis[6(l-methylcyclohexyl)-p- 0. 1

C 650 15 Dister of 3,3-thiodipropionic acid and 3-hydroxy-2,2,4-trimethylpentyl isobutyrate. 0. 5 2 3 4 2,2'-mefihylenebis[6(l-methyl-cyclohexyl)-p- 0. 3

creso It should be noted that samples 1, 5, 6, 8, 9, 11, 12, 14 and 15 correspond in formulation to the specific compositions of Examples 2-1 0, respectively.

These data of Table I demonstrate that at a concentration of about 0.5% by weight based on the poly-u-olefin, the diester of 3,3'-thiodipropionic acid and 3-hydroxy-2, 2,4-tri-methylpentyl isobutyrate is an efiective stabilizer for poly-a-olefins such as polypropylene. Indeed, comparison of the data of sample 1 with the data of sample 2 shows that at equal concentrations the diester of this invention is substantially more effective as a poly-wolefin stabilizer than dilauryl 3,3'-thiodipropionate, a diester which is a well-known, widely used, poly-a-olefin stabilizer and which is representative of the previously known diesters of 3,3- thiodipropionic acid.

The data of Table I also indicate the synergism of the diester of this invention and various sterically hindered phenols. This can be seen by comparing the data of samples 5 and 6 with the data of samples l and 3, the data of samples 8 and 9 with the data of samples 1 and 7, the data of samples 11 and 12 with the data of samples 1 and 10, and the data of samples 14 and 15 with the data of samples 1 and 13.

The efficacy of the diester of 3,3'-thiodipropionic acid and 3 hydroxy 2,2,4 trimethylpentyl isobutyrate as a plasticizer is demonstrated by the data of Table II. To obtain these data three samples of a conventional, crystalline polypropylene were procured. To two of the samples was added the diester of 3,3'-thiodipropionic acid and 3-hydroxy-2,2,4-trimethylpentyl isobutyrate. The quantity of the diester in the case of one of the samples was about 5% by weight of the resulting composition. The quantity of the diester in the case of the other sample was about 10% by weight of the resulting composition. Each sample was then milled at 190 C. for 10 minutes. The milled samples were then granulated and test specimen of the samples prepared by injection molding on a 2-3 ounce Impco molding machine. Various, conventional, physical measurements were then made on the test specimens. The

measurement data and other information are tabulated in the following Table II.

TABLE II Sample No.

Sample Components:

Crystalline polypropylene (percent by weight of sample) 100 95 Diester of 3,3-thiodipropionic acid and 3- hydroxy-2,2,4-trimethylpentyl isobutyrate (percent by weight of sample). U... Fl0W Rate 3. 50 7.25 12.8 Density .9092 9100 .9109 Tensile Strength per square inch at y1 ld 4,460 4, 100 3, 980 Stifi'ness in Flexure 145,000 120,000 110,000 Brittleness Temperature, C 15 Vicat Softening Point, C 146.0 104 .0 140. 2

Samples 2 and 3, it will be observed, correspond in composition to the formulations of Examples 11 and 12, respectively.

These data of Table II show the improvement in properties, particularly in brittle point, obtained in adding the diester of 3,3-thiodipropionic acid and 3-hydroxy-2,2,4- trimethylpentyl isobutyrate to an isotactic poly-a-olefin such as crystalline polypropylene. At no stage of the testing of samples 2 and 3 was there any evidence of incompatibility of the diester of this invention. Hence, as the data of Table II demonstrate, not only is the diester of 3,3-t'hiodipropionic acid and 3-hydroxy-2,2,4-trimethylpentyl isobutyrate, an outstandingv stabilizer for poly-aolefins such as polypropylene but also an outstanding plasticizer for poly-a-olefins such as polypropylene. A feature of advantage of the diester of this invention is its liquid state at normal temperatures. Such a state is desired since it enables the additive to be added to the poly-a-olefin by metering, a desired procedure.

Thus, there is provided a new, poly-a-olefin stabilizerplasticizer. Moreover, there is provided a poly-m-olefin composition protected against oxidative degradation. In addition, there is provided a crystalline poly-rx-olefin composition having a lower brittle point than the crystalline poly-a-olefin itself.

Other features, advantages and embodiments of the invention will be apparent to those in the exercise of ordinary skill in the art after reading the foregoing disclosure. In this connection, while this invention has been described in considerable detail relative to specific embodiments thereof, variations and modifications of these embodiments can be effected within the spirit and scope of the invention as disclosed and claimed.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. The diester of 3,3'-thiodipropionic acid and 3-hydroxy-2,2,4-trimethylpentyl isobutyrate.

References Cited UNITED STATES PATENTS 7/1951 Smith et al 260-537 6/1953 Harman et al 260-481 OTHER REFERENCES Villani et aL, J. Am. Chem. Soc., vol. 68, 1675 (1946). 

